Preparation of [bis(amido)-phosphine] and [amido-phosphine sulfide or oxide] hafnium and zirconium complexes for olefin polymerization

New phosphine-based bidentate ligands, 2-Me-8-Ph2P(X)C9H8NH (3, X = 0; 4, X = S) and N R 2 Ph2P(X) C6H4NH (5, R = Et, X = 0; 6, R = Me, X = S; 7, R = Et, X = S) were prepared via ortho-lithiation of 1,2,3,4tetrahydroquinaldine (2-Me-C9H9NH) and aniline derivatives (N-R-C6H8NH). Reaction of the ortholithiated compounds with 0.5 equiv of PhP(OPh)2 afforded the bis(amido)-phosphine ligands (2-MeC9H8NH-8-yl)2PPh (8) and (N-R-C6H4NH-2-yl)2PPh (9, R = Me; 10, R = Et). Using these ligands, [amidophosphine oxideiFIRCH2Ph13, [amido-phosphine sulfide]Hf(CH2Ph)3, [bis(amido)-phosphinelMX2 (M = Hf, Zr; X = CH2Ph, Cl, Me), and [amido-phosphine-amine1MCI3 complexes were prepared. The molecular structures of [amido-phosphine sulfideIHRCH2Ph)3 (13) (prepared using 6), [bis(amido)phosphinelZrMe2 (22) (prepared using 8), and [amido-phosphine-amine1MCI3 (23, M = Hf; 24, M = Zr; prepared using 9) were confirmed by X-ray crystallography. Most of the prepared complexes exhibited negligible or low activity for ethylene/1 -octene copolymerization. The [amido-phosphine sulfide] Hf(CH2Ph)3 complex (13) exhibited relatively high copolymerization activity (19 x 106 g/mol-Hf h); however, this activity was unsatisfactory compared to that of the related [amido-phosphine1HRCH2Ph)3 complexes (up to 48 x 106 g/mol-Hf h). (c) 2014 Elsevier BY. All rights reserved.